FI78596C - Method for controlling crop-infecting fungi and in process using fungicidal composition - Google Patents

Description

78596

The present invention relates to a process for controlling or inhibiting the growth of fungi using branched aminoalkanoic acid phosphoric acid phosphoric acid phosphonic acid phosphonic acid fungicidal compositions. The compounds are particularly suitable in the control of fungal diseases of plants. The invention also relates to compositions containing certain of these compounds.

The use of certain straight chain aminoalkanephosphonic acid compounds as fungicides is known in the art. U.S. Patent 3,764,677 describes the use of a particular ester of a specific straight chain aminoalkanephosphonic acid having fungicidal properties, namely diethyl 6-aminoethylphosphonate. Other diesters of straight chain aminoalkanephosphonic acids, namely alkyl and propynyl esters of aminomethylphosphonic acid, are also known to have fungicidal activity, as disclosed in SU Patent 557,579.

In accordance with the present invention, it has been found that branched aminoalkanephosphonic acids and aminoalkanephosphonic acid derivatives are valuable fungicides which are particularly useful as fungicides against phytopathogenic fungi. They can be used in agriculture and horticulture, e.g., as seed dressings, leaf sprays, etc. In this presentation, branched aminoalkanephosphonic acid and phosphonic acid derivatives refer to aminoalkanephosphonic acids and phosphonic acid substituents containing at least one alkoxy substituent containing at least one alkanoic acid.

The branched aminoalkanephosphonic acids and their derivatives used in accordance with the present invention have the following general formula HO 0 {*, r

\ H 1, / 1 P-C (C H,) N

/ I? n \ HO R3 R? wherein R 1 and R 2 are, independently, hydrogen or an alkyl group having 1 to 8 carbon atoms; n is an integer 0, 1, 2 or 3; R 1 is an alkyl group having 1 to 12 carbon atoms and R 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms; and salts thereof.

The active compounds of the above formula may also be in the form of their acid addition salts, which salts are acceptable in view of the intended use.

Branched aminoalkanephosphonic acids can be prepared, e.g., by condensing alkyl carbamates with aldehydes and triphenyl phosphite, as described in Tetrahedron Letters No. 32, 1977, pages 2823-2824. The salts referred to herein are metal salts, ammonium salts, salts of amines and quaternary ammonium compounds and acid addition salts are prepared by methods known per se, e.g. as shown in the examples. Esters of phosphonic acids can be prepared, for example, by condensing the acyl phosphate with hydroxylamine and finally carrying out the reduction. Half esters can be prepared from diesters using ammonia.

Particularly preferred are salts or free acids of aminoalkanephosphonic acids. It is further preferred that R f 3 78596 and 1 * 2 are a lower alkyl group having 1 to 4 carbon atoms and most preferably hydrogen. As stated above, n is an integer from 0 to 3 and suitably 0-2. An important feature of the compounds used in accordance with this invention is that the α-position of the phosphonium group is substituted with one or two alkyl groups. The number of carbon atoms in these alkyl groups, R 3 and R 2, is preferably at most 8, and most preferably at most 5. If there are two branches, the total number of carbon atoms is preferably at most 8 and most preferably at most 5. Thus, preferred compounds are those containing short branch chains. The use of compounds having only one α-substitution is particularly preferred.

The active compounds may, as indicated above, be in the form of their acid addition salts, which salts are acceptable in view of the intended use.

In this case, salts of organic acids can be used, but the acid addition salts are preferably salts of mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, etc.

Metal salts are, above all, alkali metal and alkaline earth metal, copper, cobalt, zinc, tin and aluminum salts. Salts of amines include salts of primary, secondary and tertiary amines which are aromatic, such as salts of aniline and alpha-naphthylamine, salts of aliphatic or cycloaliphatic amines with higher or lower aliphatic groups, and further cyclic amine salts, such as e.g. salts of pyrrolidine and the like, and polyamine compounds having one or more amine groups to form salts with phosphonic acid. Quaternary ammonium salts of aminophosphonic acids include salts of short-chain quaternary ammonium compounds having from 1 to 5 carbon atoms 4,78596, such as, for example, tetramethylammonium compounds and tetrabutylammonium esters of dimethyl ammonium compounds and quaternary ammonium compounds such as one or more salts of benzyldimethylalkylammonium compounds in which the alkyl chain contains from about 6 to about 20 carbon atoms, and the corresponding quaternary ammonium compounds contain one or more alkylene groups.

This invention relates to a method of destroying or inhibiting the growth of crop-contaminating fungi, comprising contacting fungi, materials or hosts which are susceptible to or already contaminated with a fungal infection with a branched aminoalkanephosphonic acid or phosphonic acid compound as defined above. The compounds are used in amounts effective to kill or inhibit the growth of the fungi in question, the dose being determined depending on the desired protection, the material to be treated, the method of treatment, etc.

Of the compounds used as fungicides according to the present invention, those in which n is 0 have been found to have very good fungicidal activity, and in particular those compounds having one ethyl branch, i.e. 1-Aminopropanephosphonic acid and its salts.

Branched aminoalkanephosphonic acids and phosphonic acid derivatives are primarily intended for the control of phytopathogenic fungi and thus for use in agriculture and horticulture.

In the control of phytopathogenic fungi, the compounds can be used to protect seeds, fruits, bulbs, the press and seedlings. The compounds and compositions containing an active amount of the compounds are particularly useful in agriculture, and in particular as seed dressings and also as foliar fungi.

The compounds are soluble in water, the solubility depends on the structure and pH, and can generally be used as water-based preparations. They can also be used as preparations obtained with conventional carriers and diluents. They can be incorporated into solid preparations such as powders, granules and pellets containing as carriers e.g. talc, clay, silicates, etc. Liquid preparations contain diluents, e.g. water and / or solvents such as ethanol, ethyl acetate, glycols, vegetable oils, dimethylformamide, N-methylpyrrolidone, etc. In the preparation of the active compounds of this invention, conventional additives and excipients can be combined with powders, dusts and liquid preparations. Examples of these are surfactants, wetting agents, stabilizers, etc. The active compounds of this invention are also compatible with other fungicidal agents and other agents having biological activity, such as insecticides, and may be used in combination with such agents if desired. The active ingredient concentration of the preparations described above 6 78596, when used in agriculture, is generally 1 to 60% by weight.

The compounds have proven to be very effective against fungi of the genus Drechslera, Septoria nodorum, Ustilaqo hordei1 and other fungi which damage the grain and can thus be used advantageously as seed dressings.

In addition to the use of the branched aminoalkanephosphonic acids and phosphonic acid derivatives described above, this invention also relates to certain compositions containing branched aminoalkanephosphonic acids and aminoalkanephosphonic acid compounds which are used as fungicides.

Thus, the invention relates to fungicidal compositions suitable for the control and monitoring of phytopathogenic fungi, which contain customary inert carriers and diluents and optionally customary additives and, as active ingredient, a salt of 1-aminopropanephosphonic acid or an acid addition salt thereof.

The invention thus relates to fungicidal compositions for controlling and controlling phytopathogenic fungi which contain customary inert carriers and diluents, and optionally conventional additives and as active ingredient of the general formula, HO 0 R, R, \ ll I * / 2 / pi <CVn \ HO R3 A salt of a compound of R 1 wherein R 1 and R 2 are independently hydrogen or an alkyl group having 1 to 8 carbon atoms, preferably both R 1 and R 2 are hydrogen; n is an integer 0, 1, 2 or 3, preferably 0-2; R 1 is an alkyl group having 1 to 12 carbon atoms and R 4 is hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 4 is preferably hydrogen; or acid addition salts thereof.

Salts of these acids in the compositions include metal salts, ammonium salts, salts of amines and quaternary ammonium compounds.

Of the above compositions, those in which the active ingredient is a salt are preferred. Metal salts include, for example, salts of alkali metals, alkaline earth metals, copper, cobalt, zinc, tin and aluminum. Salts of amines include salts of primary, secondary and tertiary amines which are aromatic, aliphatic or cycloaliate containing higher or lower aliphatic groups, and further salts include salts of cyclic amines such as morpholine and pyrrolidine and the like. Amines 8,78596 include mono-, di- and polyamines. Quaternary ammonium compounds capable of forming salts with branched aminoalkanephosphonic acids; are short chain / quaternary compounds such as e.g.

5 tetrabutylammonium compounds and quaternary compounds containing one or more hydrophobic groups, the other groups being, for example, shorter alkyl or hydroxyalkyl groups. These quaternary ammonium compounds may be, for example, alkyl-trimethyl-ammonium compounds, dimethyldialkylammonium compounds, benzyl-dimethyl-alkyl-ammonium compounds in which the alkyl chain contains 6 to 20 carbon atoms, and quaternary ammonium compounds containing corresponding alkylene groups.

The following examples further illustrate the invention, but are not intended to limit the invention.

Parts and percentages refer to parts by weight and percentages by weight unless otherwise indicated.

Example 1: Preparation of 1-aminopropanephosphonic acid

Ethyl carbamate (4.45 g), triphenyl phosphite (15.5 g) and propanal (4.06 g) were heated to reflux (1 hour) together with acetic acid (10 ml). Concentrated hydrochloric acid (50 ml) was added and the mixture was heated to reflux (6 hours), after which it was allowed to cool. The aqueous phase was separated, washed with benzene (20 ml) and evaporated to dryness. The residue was dissolved in methanol (40 ml) and propylene oxide was added until the pH was 6. The crude phosphonic acid was filtered and recrystallized from water / methanol to give fine white crystals of 9,78596 (4.2 g, 60.4%), m.p. was 264-266 ° C.

Example 2: Preparation of 1,6-diaminohexane di- (1-aminopropanephosphonic acid) salt 1-Aminopropanephosphonic acid (3.95 g, 28.4 mmol) and 1,6-diaminohexane (1.65 g, 14.2 mmol) were dissolved in water. (40 ml), after which the water was distilled off. Ethanol (50 ml) was then added and distilled off. The residue was dried in a vacuum oven at 50 ° C (4 hours) to give the above salt as a fine crystalline solid (5.5 g, 98.2%) with a melting point of 244-250 ° C.

Example 3; Preparation of 1-aminopropanephosphonic acid tetrabutylammonium-15 salt To 1-aminopropanephosphonic acid (2.91 g, 20.9 mmol) and tetrabutylammonium bromide (6.74 g, 20.9 mmol) were added water (50 mL), propylene oxide (20 mL) and water ( 50 ml). The resulting solution was then heated at 50 ° C (0.5 h) and allowed to cool. The volatiles were evaporated, dried in a vacuum oven at 50 ° C (6 hours) and further on silica gel (4 days) to give the title compound as a colorless, viscous oil (7.5 g, 94.2%).

Example 4: Preparation of 1-aminopropanephosphonic acid copper salt 1-Aminopropanephosphonic acid (5.251 g, 37.8 mmol) and 10,78596 copper acetate monohydrate (7.612 g, 37.8 mmol) were dissolved in water (50 mL) and water was distilled off. Water (50 ml) was added to the residue and the solid was filtered, washed with acetone (2 x 20 ml) and dried in a vacuum oven at 60 ° C (3 hours) to give the desired copper salt as a blue-green powder (6.9 g, 90.2 %).

Example 5: Preparation of 1-aminopropanephosphonic acid morpholine salt 1-Aminopropanephosphonic acid (4.01 g, 28.8 mmol) and 10 morpholine (5.02 g, 57.7 mmol) were dissolved in water (20 mL) and ethanol (20 mL) was added. The solvents and excess amine were evaporated, acetone (50 ml) was added and the solid was filtered, washed with acetone (50 ml) then dried in a vacuum oven at 60 ° C for 15 (4 hours) to give the morpholine salt of 1-aminopropanephosphonic acid (5.5 ml). g, 84.4%) with a melting point of 62-64 ° C.

Salts of the following amines were prepared in a similar manner, yields and melting points are given in parentheses.

3-hydroxypropylamine (98.8%, 156-160 ° C); Cyclohexylamine (96.3%, 260-264 ° C); pyrrolidine (86.5%, 76-78 ° C); diethylamine (95.5%, 84-88 ° C); piperazine (87.4%, 98-108 ° C); hexylamine (94.3%, 266-268 ° C); 25 N, N-dimethylethanolamine (89.6%, 260-264 ° C).

All 13 L salts prepared according to Examples 2-5 were characterized and identified by C- and H-nuclear magnetic resonance spectroscopy.

11,78596

Example 6:

The fungicidal activity of the following compounds was tested:

O ^ y 4J

Il l'y (O H), F - C - N H _ 2 I 2 13 «j

1) C Hj H

2) C? H5 H

3) CH 2 CH 2) 2 H

A) c7h15 h 5) CH2 C Hj 6) C2H5 C2H5 7) CH (CH3> 2 CHj

8) CjH7 H

9) C4H9 H

10) C5Hn H

11) C2H5 H as potassium salt 12) C2H5 H as copper (II) salt

The activity of the substances was examined using 5 mycelial growth inhibition assays on agar, according to the following method.

The substances were dissolved in sterilized potato dextrose agar (PDA) to a concentration of 500 ppm.

The mixture was then poured into ordinary petri dishes 9 cm in diameter. An agar disc (5 mm in diameter) with live, growing mycelium (cultured PDA) was placed in the center of each petri dish. Incubation was performed at 28 ° C for 1-3 weeks, depending on the growth rate of the fungi in question, after which the growth zone was measured and compared to untreated plates.

12,78596

The effect was tested against Drechslera sativa1a with some compounds and against Drechslera teriva1a with some.

The table shows the results according to the following scale: 5 0 = growth inhibition 0 - 25% 1 = growth inhibition 26 - 50% 2 = growth inhibition 51 - 75% 3 = growth inhibition 76 - 100%

Table

Compound D. control of sativa 1 3 2 3 3 3 4 3 5 3 6 2 7 3 Control of D. teres 8 3 9 3 10 2 11 3 12 2 10 In the same manner as above, the efficacy of some compounds was tested at a dose of 500 ppm, using Fusarium culmorum as test organism. The compounds tested were numbers 8), 9) and 10) and the results obtained with them were 3, 3 and 2, respectively.

13 78596

In a similar manner, the salts of compound 2) were also tested against Rhizoctonia solani at a dose of 300 ppm. The salts were as follows: a) diethylamine salt, b) cyclohexylamine salt, c) morpholine salt and d) pyrrole-5 dine salt, all of which gave result 3.

Example 7:

The efficacy of some compounds of the invention against Drechslera teres was tested in in vivo tests.

The tests were performed according to the Osmos method. In this method, the pickled seeds are placed on a filter paper moistened with a buffered sugar solution. The filter papers are then placed in covered, transparent plastic dishes. The plates are placed in a thermostatically controlled cabinet maintained at 22 ° C and varying between 12 hours light time and 12 hours dark time.

The evaluation was performed after one week. The surviving seed appeared to have grown a fungal filament that formed a spot, but the seed had not germinated due to osmotic pressure. Seeds with a live fungus were identified by a color test. The method is quite accurate and all seeds with a live fungus were counted, even seeds that had received a very weak infection that would not have been observed in a growing plant. The results of test 25 are presented as a percentage of control, with the infection of untreated seed, in each test, being 100%.

The following salts of 1-aminopropanephosphonic acid were tested at a dose of 2 ml of an aqueous solution (20% active ingredient) per person: 14,78596 a) cyclohexylamine salt b) hydroxypropylamine salt c) morpholine salt d) pyrrolidine salt 5 e) diet

The results were as follows: a) 64 b) 26 c) 74 10 d) 92 e) 47

Example 8; In this example, the efficacy of 1-aminopropanephosphonic acid as a leaf fungicide was investigated: 15 varieties of barley Agneta (6-sided barley) were cultivated in normal soil to step 12 (decimal code for growth steps) within 9 days. The growing conditions were lighting at 10,000 lux for 8 hours and a temperature of 15-20 ° C. Erysiphe graminis 20 f.sp. obtained from infected plants. hordei mildew spores were shaken on uninfected plants. Incubation was performed in a humidity room at 100% humidity for 24 hours at 17 ° C. The plants were then transferred back to the greenhouse. The infection began to appear after 5 days 25 and the results were read after 8 days.

The test was a preventive test in which the plants had been sprayed before infection with the active compound. The plants, 10 in each pot, were sprayed with an aqueous solution containing 500 ppm aminophosphonic 78596 acid. The solution contained a wetting agent. 6 pots, i.e. 60 plants, were used for this test. For comparison, a commercial product (Forbel 750 g active ingredient / hectare) was used in the same manner and comparison 5 was also performed on untreated plants. The number of downy mildew spots after incubation with plants was counted and the results were as follows: untreated plants 14 (potency = 0%), 3 (potency = 75%) treated with the agent of this invention, 0 (potency = 100%) treated with a commercial product.

Example 9: In these field tests, the efficacy of 1-aminopropanephosphonic acid against several different fungi was tested.

1. Septoria nodorum (leaf and green spot disease) 15 Material and method: Winter wheat, Holme variety with an inherently severe S. nodorum fungal infection, was used in the test. Wheat seed was weighed and treated with a preparation containing a compound at a dosage ratio of 2 ml / person (20% active ingredient).

20 The seed treatment was carried out in a seed treatment machine. The seed was sown in the autumn in randomized block plots (1.3 x 10 m / plot and 4 parallel).

When the plants had 2-3 leaves, the plants were dug up at a distance of 25 two meters / Plot and the contamination of the cotyledons was assessed.

2. Ustilago hordei (barley cache)

Material and method: Barley, variety Birka, was infected with 16,78596 using 4 kg cereal spores / seedling. Barley seed was weighed and treated using 2 ml of preparation (20% active ingredient) / person. In the spring, the seed was sown in randomly selected test plots.

5 The number of infected cones was estimated from 9.4 to 11.4 square meters / plot.

3. Drechslera teres (net spot disease)

Material and method: Barley seed, a variety of Tellus with an inherently severe D. teres fungal infection, 10 was used in these tests. The seed was treated as described above and sown in the spring.

In the 2-leaf stage, an assessment was performed of the plants with the main contamination on the first leaf.

Contamination is presented as figures compared to 15 contamination with untreated plants (= 100% with untreated plants). The potency of the compound is expressed as percentage control (= 0% on untreated plants) and the results are shown in the table. When the tests were performed at two different sites, the results 20 are given separately.

Further, field experiments investigated the effect of 1-aminopropanephosphonic acid against several other fungi.

4. Tilletia caries (winter wheat stink)

Material and method: Winter wheat, Holme variety, infek-25 was fed using 5 g cereal spores / seed. Wheat seed was weighed and treated using 2 ml of composition (20% active ingredient) / person. Seed treatment 17,78596 was performed in a seed treatment machine. The seed was sown in the autumn in randomly selected plots (2 m x 16 m / Plot and 4 parallel).

The number of diseased cones was calculated from an area of 10 square to 5 meters / plot.

5. Drechslera graminea (barley leaf virus)

Material and method: Barley seed, Agneta variety, which had a naturally strong D. graminea fungal infection, was used in these tests. The seed was treated as described above with 2 ml of composition / seed, and sown in spring.

In 5-6 leaf stages (Freekes magnitude No. 6, decimal code No. 31-32), the number of diseased plants per square meter was counted.

15 6. Drechslera avenae (oat necrosis)

Material and method: Oat seed, variety Selma, which naturally had D. avenae fungal infection, was used in these tests. The seed was treated at a dose ratio of 2 ml / seed person (20% active ingredient).

20 The number of plants diseased in the 2-leaf stage was calculated per square meter.

7. Ustilago avenae (oat fly)

Material and method: Oat seed, Hedvig variety, was infected using 3 g of grain spores / 3 liters of 25 water (wetting infection with vacuum). The infected seeds were dried in thin layers at room temperature 7,896 until the water content was about 15%. Dry, infected seed was treated using 2 ml of composition (20% active ingredient) / seed in a seed mirror.

5 The treated seed was sown in the spring in randomly selected plots (1.35 m x 8 m / Plot and 4 parallel). The number of infected cones was counted and the results are given as a number per three square meters.

10 The results of these field experiments are given in the table in the same way as above.

Table

Fungus attack control

Septoria nodorum treated 27 73

Ustilago hordei dog box I

dealt with 22 78

dog box II

dealt with 28 72

Drechslera teres dog box I

processed 0 100

dog box II

treated 0.3 99.7

Tilletia caries treated 18 82

Drechslera graminea dog box I

processed 4 96 78596 19

Fungus attack control

dog box II

processed 1 99

Drechslera avenae dog box I

processed 0 100

dog box II

processed 1 99

Ustilago avenae dog box I

dealt with 4 96

dog box II

processed 5 95

In the above field experiments, the efficacy of a straight-chain aminoalkanephosphonic acid, 3-aminopropanephosphonic acid having the same number of carbon atoms, against Drechslera teres and Drechslera avenae1 was investigated for comparison. The infection control obtained with this compound was 28% and 37%, respectively.

Example 10; The effect of 1-aminopropanoic acid salts against D. graminae was studied. Seed-treated seeds were sown on plates containing moist soil mixed with sand. The plates were kept in a cold place (+ 6 ° C) for 10-12 days and then at room temperature and exposed until they had reached the 2-3-3.ehti stage. The number of 20,78596 of germinated plants and plants with typical spots on Sirkka leaves, leaves and roots were counted. The percentage contamination in each treatment is compared to the untreated (100%) and the seed pickling effect given below is expressed as a percentage relative to this.

a) 3-hydroxypropylamine salt 100% b) piperazine salt (piperazine bis-acid salt) 98% c) hexamethylenediamine salt (bis-acid salt) 100% d) hexylamine salt 98% e) dimethylethanolamine salt 100%

Example 11:

The following salts of 1-aminopropanoic acid were tested, at doses of 500 ppm against D. teres, as described in Example 6: a) isopropylamine salt, b) sec-butylamine salt, c) tetrabutylammonium salt. The evaluation and classification according to the scale given in Example 6 gave the following results: a) 3, b) 3, c) 2.

Example 12}

The following substances were tested against F. culmorum at a dose of 500 ppm as described in Example 6: a) 1-aminopropanephosphonic acid, b) diotyl 1-aminopropane phosphonate, c) diethylaminoethanephosphonate (comparison). The results were as follows: a) 2, b) 2, c) 1.

Claims (10)

1. A method for controlling crop-attacking fungi, characterized in that the fungi, materials or hosts which may be attacked by or which are already affected by harvest-attacking fungi are contacted with a compound of the general formula HO. R 2, wherein R 2 and R 2 are independently hydrogen or an alkyl group of 1-8 carbon atoms; n is a hot 0.1, 2 or 3; R3 is an alkyl group of 1-12 carbon atoms; R4 is hydrogen or an alkyl group of 1-12 carbon atoms; or with their salts or acid addition salts. 2. A process according to claim 1, characterized in that both R 2 and R 2 are hydrogen. Process according to Claim 1 or 2, characterized in that R 4 is hydrogen. 4. A method according to claim 1, 2 or 3, characterized in that n is 0. Process according to claim 1, characterized in that R 2 R 2 and R 4 are hydrogen, n is 0 and R 3 is an alkyl group having 1-5 carbon atoms. Process according to Claim 1, characterized in that the compound is 1-aminopropane phosphonic acid, its site or acid addition salt. Process according to any one of the preceding claims, characterized in that the salt is a metal compound.